JP5644476B2 - Photosensitive resin composition, cured film using the same, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Description

  The present invention relates to a photosensitive resin composition suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a cured film as an insulating film or protective film using the same, and a semiconductor device The present invention relates to a manufacturing method and a semiconductor device.

  Conventionally, polyimide-based resins, polybenzoxazole-based resins, and polyamide-imide-based resins that are excellent in heat resistance, mechanical properties, and the like have been widely used for surface protective films, interlayer insulating films, and the like of semiconductor elements of electronic devices. Among these, positive photosensitive resin compositions composed of a polybenzoxazole precursor that has high moisture resistance and can be developed with an alkaline aqueous solution and a quinonediazide compound that is a photosensitive agent have been developed. However, in recent years, with an increase in wafer diameter, in order to improve the processing capacity per unit time, improvement in sensitivity to exposure is strongly demanded. However, these resin compositions are i-line (wavelength 365 nm) of mercury lamps. The transmittance | permeability of this was low and there existed a subject that it was low sensitivity.

  As a technique for increasing sensitivity, a polyamic acid ester and / or a polyamic acid polymer with a phenolic hydroxyl group-containing thermally crosslinkable compound added (see Patent Document 1), and a polyamic acid ester with an iodonium salt added as a dissolution inhibitor (See Patent Documents 2 and 3), Polyamide added with an iodonium salt as a dissolution inhibitor (see Patent Document 4), Polyacid ester with a photoacid generator and a vinyloxy group-containing compound added (see Patent Document 5) ), A polyamic acid ester having an acid-dissociable group added with a photoacid generator (see Patent Document 6) has been developed, and when developed immediately after exposure, the desired sensitivity can be obtained. When developed after standing for several hours to several days, there was a problem that the sensitivity was remarkably lowered.

  When 1,2-naphthoquinonediazide-4-sulfonic acid ester (4-ester) is used as the photosensitive group of the quinonediazide compound of the photosensitizer, the corresponding 1,2-naphthoquinonediazide-5-sulfonic acid ester (5- It is known that high sensitivity can be obtained by i-line (wavelength 365 nm) exposure compared to ester). This is because the 5-ester compound having sensitivity to g, h, and i rays of a mercury lamp generates carboxylic acid upon exposure, whereas the 4-ester compound having sensitivity only to i ray is a carboxylic acid and a strong acid sulfone. It is said to show higher alkali solubility by generating an acid (Non-Patent Document 1). However, when a 4-ester form is used as a photosensitizer, there is a problem that the sensitivity is lowered significantly after standing after exposure as compared with the 5-ester form.

  The cause of such a decrease in sensitivity due to exposure after exposure is, for example, that the acid generated by light diffuses from the exposed area to the unexposed area, or a basic substance such as a nitrogen-containing compound present in the atmosphere. It is conceivable that the acid generated by is deactivated. The decrease in sensitivity due to exposure after exposure in a chemically amplified resist using a photoacid generator is mainly due to these causes. As a method of suppressing this, a technique of adding an additive that can be trapped without deactivating the acid generated in the exposed portion is used (for example, Patent Documents 6, 7, 8, and 9). In addition to the chemically amplified resist, a polysilsesquiazane-based positive heat-resistant photosensitive composition for use as an interlayer insulating film is used in order to suppress the influence of exposure after exposure (Patent Document 10). ).

  However, these methods are effective only when the exposure time after exposure is within several hours, and the developability after several days after exposure is remarkably lowered. Moreover, even if these methods are applied to a system of an actual quinonediazide compound and a photosensitive resin precursor composition such as a polyamide resin, there is almost no improvement in sensitivity reduction due to standing after exposure. Moreover, what added the compound which has two or more allyl groups or a vinyl group to these compositions (for example, patent document 11, 12, 13) is developed, and the hardened | cured material obtained therefrom has high chemical resistance However, there is a problem that it is difficult to withstand practical use because the cross-linking reaction proceeds with the passage of time, resulting in the loss of dimensional controllability of the pattern in the wafer surface after development. .

JP 2002-328472 A (Claim 1) JP 2001-42527 A (Claims 10 to 12) JP 2003-140340 A (Claims 2 and 14) JP 2002-169283 A (Claims 6 and 7) JP 2002-122993 A (Claim 1) JP 2002-284875 A (Claims 15 and 19) JP-A-1993-232706 (Claims 1 to 3) Japanese Patent Laid-Open No. 1993-249662 (Claim 3) JP-A-1995-146558 (Claims 1, 2, and 4) JP-A-1995-120929 (Claim 5) JP 2008-58756 A (Claim 1) JP 2008-520660 A (Claim 3) JP 2003-295431 A (Claim 1)

J. et al. J. et al. Grunwald, C.I. Gal, and S.R. Eidelman, Proc. SPIE, 1262, 444 (1990).

  In view of the above problems, the present invention is a photosensitive resin composition having excellent sensitivity and post-exposure standing stability and excellent dimensional controllability, a cured film as an insulating film or a protective film using the same, and use thereof An object of the present invention is to provide a semiconductor device.

  In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. That is, (a) polyimide, polybenzoxazole or polyamideimide, any precursor thereof or alkali-soluble resin which is a copolymer thereof, (b) quinonediazide compound, (c) any one of the following general formula (1) And (d) a photosensitive resin composition characterized by containing a solvent.

  The photosensitive resin composition of the present invention is excellent in sensitivity and post-exposure standing stability, and further has excellent dimensional controllability, a cured film as an insulating film and a protective film, and a semiconductor device using the photosensitive resin composition Can be obtained.

  The photosensitive resin composition according to the present invention includes (a) polyimide, polybenzoxazole or polyamideimide, an alkali-soluble resin which is a precursor or copolymer thereof, (b) a quinonediazide compound, (c) It contains a compound represented by any one of the above general formula (1) and (d) a solvent.

  Further, the cured film as the insulating film or protective film of the present invention is characterized by being composed of a cured product of the photosensitive resin composition described above.

  Moreover, the semiconductor device of this invention is comprised by the cured film of the photosensitive resin composition as described above, It is characterized by the above-mentioned.

  First, the photosensitive resin composition will be described.

  The component (a) used in the photosensitive resin composition of the present invention includes an alkali-soluble resin that is a polyimide, polybenzoxazole, polyamideimide, a precursor thereof, or a copolymer thereof, and the component (a) May contain 2 or more types, and may contain the copolymer which has these 2 or more types of repeating units. Among these, a polybenzoxazole precursor or a copolymer of polyimide and polybenzoxazole is preferable.

  The polyimide preferably used in the present invention can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, etc. with diamine, corresponding diisocyanate compound, or trimethylsilylated diamine. And having a tetracarboxylic acid residue and a diamine residue. For example, polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, can be obtained by dehydrating and ring-closing by heat treatment. During this heat treatment, a solvent azeotropic with water such as m-xylene can be added. Alternatively, it can also be obtained by adding a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring closure catalyst and performing dehydration and ring closure by chemical heat treatment. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and dehydrating and ring-closing by heat treatment at a low temperature of 100 ° C. or lower.

  The polybenzoxazole preferably used in the present invention can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, etc., and a dicarboxylic acid residue and a bisaminophenol residue. Have For example, polyhydroxyamide, which is one of polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, can be obtained by dehydration and ring closure by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and dehydrating and ring-closing by chemical treatment.

  Examples of the polyimide precursor preferably used in the present invention include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. For example, polyamic acid can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine. The polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment such as acid or base.

  Examples of the polybenzoxazole precursor preferably used in the present invention include polyhydroxyamide. For example, polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, and the like. Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide obtained by the above method by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compound or the like.

  The polyamideimide precursor preferably used in the present invention can be obtained, for example, by reacting diamine or diisocyanate with tricarboxylic acid, corresponding tricarboxylic acid anhydride, tricarboxylic acid anhydride halide or the like. Polyamideimide can be obtained, for example, by subjecting the precursor obtained by the above method to dehydration and ring closure by heating or chemical treatment such as acid or base.

  The copolymer of polyimide, polybenzoxazole, and polyamideimide preferably used in the present invention may be any of block copolymerization, random copolymerization, alternating copolymerization, and graft copolymerization, or a combination thereof. For example, a block copolymer can be obtained by reacting polyhydroxyamide with tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, or the like. Furthermore, dehydration and ring closure can be performed by heating or chemical treatment such as acid or base.

  The component (a) used in the present invention preferably has a structural unit represented by any one of the general formulas (2) to (5), and more preferably has a structural unit represented by (5). . Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized. The resin of the component (a) in the present invention preferably contains 3 to 1000 structural units represented by the general formulas (2) to (5) in the molecule, and more preferably contains 20 to 200.

In General Formulas (2) to (5), R ¹ and R ⁴ are tetravalent organic groups, R ² , R ³ and R ⁶ are divalent organic groups, R ⁵ is a trivalent organic group, and R ⁷ is A divalent to tetravalent organic group, R ⁸ represents a divalent to divalent organic group. R ^{1 to} R ⁸ each preferably has an aromatic ring and / or an aliphatic ring. R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. p represents an integer of 0 to 2, and q represents an integer of 0 to 10.

In the general formulas (2) to (5), R ¹ is a tetracarboxylic acid derivative residue, R ³ is a dicarboxylic acid derivative residue, R ⁵ is a tricarboxylic acid derivative residue, R ⁷ is di-, tri- or tetra- Represents a carboxylic acid derivative residue. Examples of the acid component constituting R ¹ , R ³ , R ⁵ , R ⁷ (COOR ⁹ ) _p include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, and biphenyl. Examples of tricarboxylic acids such as dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, tetracarboxylic acid as examples of pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′- Benzophenone tetracarboxylic acid, 2,2 ', 3,3'-benzophenone Lacarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-di Carboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4 -Dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5 Aromatic tetracarboxylic acids such as 1,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarboxylic acid, 1 , And the like aliphatic tetracarboxylic acids such as 2,3,4-cyclopentane tetracarboxylic acid. Among these, in the general formula (5), one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid respectively correspond to COOR ⁹ group. These acid components can be used as they are or as acid anhydrides, active esters and the like. These two or more acid components may be used in combination.

In general formulas (2) to (5), R ² , R ⁴ , R ⁶ and R ⁸ represent diamine derivative residues. Examples of the diamine component constituting R ² , R ⁴ , R ⁶ , R ⁸ (OH) _q include bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-amino-4-hydroxyphenyl). ) Sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-) Hydroxyl) biphenyl, hydroxyl group-containing diamines such as bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, and thiol groups such as dimercaptophenylenediamine Containing diamine, 3,4′-diaminodiphenyl ether, 4,4′- Aminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4 ′ -Diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) Phenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2, 2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) ) Compounds having aromatic diamines such as -4,4'-diaminobiphenyl and a part of hydrogen atoms of these aromatic rings substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, and the like, And alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components. In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.

R ^{1 to} R ⁸ in the general formulas (2) to (5) can contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or the like in the skeleton. By using a resin having an appropriate phenolic hydroxyl group, sulfonic acid group or thiol group, a positive photosensitive resin composition having an appropriate alkali solubility can be obtained.

  Moreover, it is preferable to have a fluorine atom in the structural unit of the component (a). The fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed. The fluorine atom content in the component (a) is preferably 10% by weight or more in order to sufficiently obtain the effect of preventing the penetration of the interface, and is preferably 20% by weight or less from the viewpoint of solubility in an aqueous alkali solution.

In addition, an aliphatic group having a siloxane structure may be copolymerized with R ² , R ^6, or R ⁸ as long as the heat resistance is not lowered, and adhesion to the substrate can be improved. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

  In addition, in order to improve the storage stability of the resin composition, the resin as the component (a) has an end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound at the main chain terminal. It is preferable to seal with. The introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc., as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds Product, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like; Mono-acid chloride compounds in which the carboxyl group is converted to acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene , Monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3 -Active ester compounds obtained by reaction with dicarboximide are preferred. Two or more of these may be used.

  In the resin having the structural unit represented by any one of the general formulas (2) to (4), the number of repeating structural units is preferably 3 or more and 200 or less. In the resin having the structural unit represented by the general formula (5), the number of repeating structural units is preferably 10 or more and 1000 or less. If it is this range, a thick film can be formed easily.

  The component (a) used in the present invention may be composed only of the structural unit represented by any one of the general formulas (2) to (5), or may be a copolymer with another structural unit or A mixture may be sufficient. At that time, the structural unit represented by any one of the general formulas (2) to (5) is preferably contained in an amount of 10% by weight or more, more preferably 30% by weight or more based on the whole resin. Among these, from the viewpoint of heat resistance during low-temperature firing and storage stability, the structural unit of the general formula (2) is preferably included in an amount of 20 to 200, more preferably 30 to 150. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment. Examples of such a main chain skeleton include benzimidazole and benzothiazole.

  The photosensitive resin composition of the present invention contains (b) a quinonediazide compound.

  Examples of the quinonediazide compound include a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound, and a sulfonic acid of quinonediazide to an ester bond and / or a polyhydroxypolyamino compound. Examples thereof include those having a sulfonamide bond. Although all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, it is preferable that 40 mol% or more of the entire functional groups are substituted with quinonediazide on average. . By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray. Can be obtained.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manabu Kogyo Co.), although such a novolak resin include, but are not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  Among these, it is more preferable that (b) the quinonediazide compound contains an ester with a phenol compound and a 4-naphthoquinonediazidesulfonyl group. Thereby, high sensitivity can be obtained by i-line exposure.

  The content of the (b) quinonediazide compound is preferably 1 to 50 parts by weight and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the resin (a). By setting the content of the quinonediazide compound within this range, higher sensitivity can be achieved. Furthermore, you may add a sensitizer etc. as needed.

  The photosensitive resin composition of the present invention contains (c) a compound represented by any one of the following general formula (1). Thereby, the sensitivity of the photosensitive resin composition and the post-exposure standing stability can be improved, and a photosensitive resin composition excellent in dimensional controllability can be obtained. Further, two or more types of component (c) may be used in combination. The reason why the photosensitive resin composition can be improved in sensitivity and post-exposure standing stability and further excellent in dimensional controllability by these compounds is not clear, but is represented by any one of the following general formula (1). It is expected that the viscosity and solubility of the resulting compounds are affected.

  The total content of the component (c) is preferably 0.5 to 30 parts by weight and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the resin of the component (a). By setting the total content of the component (c) within this range, a higher sensitivity can be achieved, the exposure stability after exposure is improved, and a photosensitive resin composition having excellent dimensional controllability is obtained. can get.

  The photosensitive resin composition of the present invention contains (d) a solvent. Thereby, it can be set as a varnish state and applicability | paintability can be improved.

  The solvent (d) is a polar aprotic solvent such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n -Propyl ether, propylene glycol mono-n-butyl ether, di Ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran and dioxane Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate ,Propylene glycol Esters such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl pro Pionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , Butyric acid i-pro , N-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc. aromatic hydrocarbons such as toluene, xylene , N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like can be used alone or in combination. Among these, γ-butyrolactone is preferable because it can dissolve other components well and form a coating film with good flatness.

  Although the usage-amount of said (d) solvent is not specifically limited, 50-2000 weight part is preferable with respect to 100 weight part of resin of (a) component, and 100-1500 weight part is especially preferable.

  The photosensitive resin composition of the present invention may contain a compound having at least two alkoxymethyl groups or methylol groups for the purpose of easily obtaining a cured film. By having two or more of these groups, it is possible to obtain a crosslinked structure by condensation reaction with the resin and the same kind of molecules.

  Preferred examples of such a compound include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML- PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM- MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM- BPA, TMOM-BPAF, TM M-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKACALAC MX -270, NIKALAC MX-279, NIKACALAC MW-100LM, NIKACALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained.

  The content of the compound having at least two alkoxymethyl groups or methylol groups is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, further preferably 100 parts by weight of the resin (a). It is 10 parts by weight or more, preferably 300 parts by weight or less, more preferably 200 parts by weight or less.

  Moreover, you may contain the compound which has a phenolic hydroxyl group in the range which does not make the shrinkage | contraction residual film ratio after hardening small as needed. Thereby, development time can be adjusted and scum can be improved. Examples of these compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), novolak resin, and the like. Two or more of these may be contained.

  The content of the compound having a phenolic hydroxyl group is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin of component (a).

  The photosensitive resin composition of the present invention includes surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl for the purpose of improving the wettability with the substrate as necessary. Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be contained.

  Moreover, the resin composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like. The primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

  In addition, in order to enhance the adhesion to the substrate, the resin composition of the present invention includes, as a silicon component, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as long as storage stability is not impaired. A silane coupling agent such as silane may be contained. A preferable content is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin of component (a).

  Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

  The positive photosensitive resin composition of the present invention is applied to a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, slit coating, roll coating, and the like, or a combination thereof. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying is 0.1 to 150 μm.

  In order to enhance the adhesion between the substrate such as a silicon wafer and the positive photosensitive resin composition, the substrate can be pretreated with the aforementioned silane coupling agent. For example, a solution in which 0.5 to 20% by weight of a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment or the like. In some cases, a heat treatment is subsequently performed at 50 ° C. to 300 ° C. to advance the reaction between the substrate and the silane coupling agent.

  Next, the substrate coated with the positive photosensitive resin composition is dried to obtain a positive photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the positive photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. The actinic radiation used for exposure includes ultraviolet rays, visible rays, electron beams, X-rays, and the like. In the present invention, those having a wavelength of 200 to 500 nm which is the photosensitive wavelength of quinonediazide are preferable.

  In order to form the pattern of the heat resistant resin, after the exposure, the exposed portion is removed using a developer. Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, it is preferable to rinse the pattern formed by development with distilled water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing treatment.

  Next, heat treatment is performed to form an imide ring or an oxazole ring, or a thermal crosslinking reaction is advanced to improve heat resistance and chemical resistance. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned. The heat treatment conditions in the present invention are preferably from 150 ° C. to 400 ° C., more preferably from 200 ° C. to 350 ° C.

Next, the cured film as the insulating film or protective film of the present invention will be described. A cured film composed of a cured product of the photosensitive resin composition is suitably used for applications such as a semiconductor passivation film, a protective film for semiconductor elements, and an interlayer insulating film for multilayer wiring for high-density mounting.
Next, a semiconductor device having a cured film layer obtained by forming the photosensitive resin composition of the present invention on a substrate and heating it will be described. The surface protection formed by forming the cured film of the said photosensitive resin composition on the passivation film which forms the cured film which is a hardened | cured material obtained using the photosensitive resin composition of this invention, and a passivation film Examples thereof include an interlayer insulating film formed on a film and a circuit of a semiconductor element.

  In addition, the cured film made of the photosensitive resin composition has excellent stability after being exposed to light and also has excellent dimensional controllability, so that the yield of semiconductor devices can be improved.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. First, an evaluation method in each example and comparative example will be described. For the evaluation, a photosensitive resin composition (hereinafter referred to as “varnish”) filtered in advance with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Sensitivity evaluation Using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Ltd.), varnish was applied on a silicon wafer by spin coating, and heated on a hot plate at 120 ° C. for 3 minutes. Then, it exposed using exposure machine i line | wire stepper NSR-2005i9C (made by Nikon Corporation). After the exposure, using the Mark-7 developing device, a 2.38 wt% aqueous solution of tetramethylammonium (hereinafter TMAH, manufactured by Tama Chemical Industry Co., Ltd.) is used for paddle development for 40 seconds. After repeating twice, rinsed with distilled water, shaken off and dried to obtain a pattern. The pattern was observed with a FDP microscope MX61 (manufactured by Olympus Co., Ltd.) at a magnification of 20 times, and the minimum exposure required for opening a pattern with a mask size of 5 μm was determined, and this was taken as the sensitivity, 250 mJ / cm ² Yu things ^(◎), the good (○) those of ^{251mJ / cm 2 ~500mJ / cm 2} , was 500mJ / cm ² or more impossible things (×).

(2) Evaluation of standing stability after exposure Using the coating and developing apparatus Mark-7, a varnish was applied on a silicon wafer by a spin coating method and heated on a hot plate at 120 ° C. for 3 minutes. The exposure was performed using the exposure machine i-line stepper NSR-2005i9C. Thereafter, the silicon wafer was left in a yellow room maintained at room temperature of 23 ° C. and humidity of 45% for 100 hours, and then, using the Mark-7 developing device, a paddle method using a 2.38 wt% TMAH aqueous solution. Then, development with a paddle time of 40 seconds was repeated twice, rinsed with distilled water, and then shaken and dried to obtain a pattern. Observe the pattern with an optical microscope in the same way as in (1), determine the minimum exposure required for opening a pattern with a mask size of 5 μm, and compare this with the sensitivity determined in (1) to obtain the overall value of the rate of change. Is more than 15% is unstable (×), more than 10% is 15% or less stable (◯), 10% or less is more stable (（).

(3) Evaluation of dimensional controllability Using the coating and developing apparatus Mark-7, varnish was applied onto a silicon wafer by spin coating, heated on a hot plate at 120 ° C for 3 minutes, and then exposed to light. The same pattern was exposed to the same pattern at 86 locations on one silicon wafer using an i-line stepper NSR-2005i9C. Thereafter, using the Mark-7 developing device, development with a paddle method of 40 seconds was repeated twice using a 2.38 wt% TMAH aqueous solution, rinsed with distilled water, shaken and dried. Got the pattern. The pattern was observed with an optical microscope in the same manner as in (1), the pattern size with a mask size of 5 μm was measured at 86 locations, and the difference between the maximum size and the minimum size of the obtained pattern was determined. ) More than 1 μm and less than 3 μm were judged as good (◯), and more than 3 μm as unacceptable (x).

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone and 17 of propylene oxide. It was dissolved in 0.4 g (0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the reaction was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula (6).

Synthesis Example 2 Synthesis of Alkali-Soluble Resin (A-1) 6.3 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manac Co., Ltd., hereinafter referred to as ODPA) under a dry nitrogen stream (0.02 mol) was dissolved in 100 g of N-methylpyrrolidone (hereinafter referred to as NMP). Here, 9.07 g (0.015 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 0.25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 25 g of NMP. And reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.87 g (0.008 mol) of 4-aminophenol as an end-capping agent was added together with 5 g of NMP, and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the stirring, the solution was cooled to room temperature and then poured into 1 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a copolymer of a polyimide precursor and a polybenzoxazole precursor (A -1) was obtained.

Synthesis Example 3 Synthesis of Alkali-Soluble Resin (A-2) Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted. Cooled to -15 ° C. 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to γ-butyrolactone (GBL). ) A solution dissolved in 25 g was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a target polybenzoxazole precursor (A-2) which is an alkali-soluble resin.

Synthesis Example 4 Synthesis of Alkali-Soluble Resin (A-3) Under a dry nitrogen stream, 51.3 g (0.085 mol) of hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) Tetramethyldisiloxane (SiDA, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.24 g (0.005 mol) and 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 g (0.02 mol) were dissolved in 200 g of NMP. . ODPA 31.0g (0.1 mol) was added here, and it stirred at 40 degreeC for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., DFA) with 5 g of NMP was added dropwise over 10 minutes. After dropping, stirring was continued at 40 ° C. for 2 hours. After completion of the stirring, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Furthermore, it wash | cleaned 3 times with 2 L of water, and the collected polymer solid was dried with the 50 degreeC vacuum dryer for 72 hours, and the polyimide precursor (A-3) which is the target alkali-soluble resin was obtained.

Synthesis Example 5 Synthesis of quinonediazide compound (B-1) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26 .86 g (0.10 mol) and 14.43 g (0.05 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 50 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (B-1).

Synthesis Example 6 Synthesis of quinonediazide compound (B-2) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 4-naphthoquinonediazidesulfonyl acid chloride 26 .86 g (0.10 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (B-2).

Synthesis Example 7 Synthesis of quinonediazide compound (B-3) 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidesulfonyl acid chloride 26 under a dry nitrogen stream .86 g (0.10 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (B-3).

Example 1
To 5 g of the alkali-soluble resin (A-1) obtained in Synthesis Example 2, 1.0 g of the quinonediazide compound (B-1) and 0.2 g of the compound having the following formula (C-1) structure are used as the solvent (D). After being dissolved in 10 g of γ-butyrolactone, it was filtered through a 1 μm filter made of polytetrafluoroethylene (manufactured by Sumitomo Electric Industries, Ltd.) to prepare a varnish, which was evaluated by the above method.

Example 2
A varnish was prepared in the same manner as in Example 1 except that 0.9 g of the following formula (C-2) was used instead of (C-1) used in Example 1, and the same evaluation was performed.

Example 3
A varnish was prepared in the same manner as in Example 1 except that 0.1 g of the following formula (C-3) was used instead of (C-1) used in Example 1, and the same evaluation was performed.

Example 4
A varnish was prepared in the same manner as in Example 1 except that (A-2) obtained in Synthesis Example 3 was used instead of (A-1) used in Example 1, and the same evaluation was performed. .

Example 5
A varnish was prepared in the same manner as in Example 1 except that (A-3) obtained in Synthesis Example 4 was used instead of (A-1) used in Example 1, and the same evaluation was performed. .

Example 6
A varnish was prepared in the same manner as in Example 1 except that 1.8 g of (B-2) obtained in Synthesis Example 6 was used instead of (B-1) used in Example 1, and the same evaluation was made. Went.

Example 7
A varnish was prepared in the same manner as in Example 1 except that 0.6 g of (B-3) obtained in Synthesis Example 7 was used instead of (B-1) used in Example 1, and the same evaluation was made. Went.

Example 8
A varnish was prepared and evaluated in the same manner as in Example 1 except that (C-1) used in Example 1 was changed to 1.5 g.

Comparative Example 1
To 5 g of the resin (A-1) obtained in Synthesis Example 2, 1.0 g of the quinonediazide compound (B-1) was dissolved in 10 g of γ-butyrolactone as a solvent (D), and then 1 μm of polytetrafluoroethylene It filtered with the filter (made by Sumitomo Electric Industries, Ltd.), the varnish which does not contain (C-1) was created, and the same evaluation was performed.

Comparative Example 2
A varnish was prepared and evaluated in the same manner as in Example 1 except that (C-1) used in Example 1 was changed to allyl benzoate represented by the following formula (7).

Comparative Example 3
A varnish was prepared and evaluated in the same manner as in Example 1 except that (C-1) used in Example 1 was changed to triallyl trimellitic acid represented by the following formula (8).

Comparative Example 4
A varnish was prepared in the same manner as in Example 1 except that (C-1) used in Example 1 was changed to tetraallyl pyromellitic acid represented by the following formula (9), and the same evaluation was performed.

  The composition of the evaluation varnish is shown in Table 1, and the evaluation results are shown in Table 2.

Claims (8)

(A) Polyimide, polybenzoxazole or polyamideimide, any one of these precursors or an alkali-soluble resin that is a copolymer thereof, (b) a quinonediazide compound, (c) any one of the following general formula (1) A photosensitive resin composition comprising: a compound to be prepared; and (d) a solvent.

The (a) polyimide, polybenzoxazole or polyamideimide, any precursor thereof, or an alkali-soluble resin as a copolymer thereof is a polybenzoxazole precursor or a copolymer of polyimide and polybenzoxazole. 2. The photosensitive resin composition according to claim 1, wherein: (C) The total content of the compound represented by any one of the general formula (1) is (a) polyimide, polybenzoxazole, polyamideimide, any one of these precursors or a copolymer thereof. The photosensitive resin composition according to claim 1 or 2, wherein the amount is 0.5 to 30 parts by weight with respect to 100 parts by weight of a certain alkali-soluble resin. The photosensitive resin composition according to claim 1, wherein the (b) quinonediazide compound contains a 4-naphthoquinonediazidesulfonic acid ester of a phenol compound. The photosensitive resin composition according to claim 1, wherein the solvent (d) contains γ-butyrolactone. A cured film comprising a cured product of the photosensitive resin composition according to claim 1. A method for producing a semiconductor device, comprising: applying a photosensitive resin composition according to any one of claims 1 to 5 on a substrate and then heating to form a cured film layer. A semiconductor device comprising a cured film layer obtained by forming the photosensitive resin composition according to claim 1 on a substrate and heating the composition.